Germicidal paper



United States Patent Ofi" 3,2216% Patented Jan. 4, 1966 3,227,614GERNHCIDAL PAPER Fred F. Scheuer, Bronx, N.Y., assignor to DustllrinPro-d- ;ctsii Inc., New York, N.Y., a corpuration of New No Drawing.Filed Sept. 29, 1960, Ser. No. 59,150

13 Claims. (Cl. 1167-84) This invention relates to a bacteriostatic orgermicidal paper or tissue. More particularly, it relates to agermicidal or bacteriostatic paper or tissue which may be used wet ordry to wipe surfaces to render them germicidal or bacteriostatic.

} It is an object of the present invention to provide a germicidal orbacteriostatic paper which is disposable, economical and effective inrendering surfaces bacteriostatic or germicidal when contacted with thispaper. (This is to be contrasted with the common use of untreated paperwhich may be already contaminated with pathogenic organisms and whichtransmits these organisms to asurface to be cleaned.)

It is a further object of the present invention to provide a method forpreparing such paper.

Other and more detailed objects will be apparent from the followingdescription and claims.

The inexpensive, disposable bacteriostatic paper or tissue of thepresent invention is of great value both for civilian and military uses.

Dry it is useful in hospitals, doctors offices, laboratories, etc. asdust Wipers, which impart the areas wiped with potential bacteriostaticprotection. In this manner the danger of the spread of dust-borninfection in hospitals and doctors offices can be reduced. Another useis wiping telephone receivers, keys of typewriters and electronicequipment, industrial safety equipment such as the exposed surfaces ofgas masks, goggles, welders and riveters safety masks, respirators,inhalators, safety shoes and boots, etc. in order to render themsanitary.

Wet it is useful in hospitals, doctors ofiices, laboratories and allplaces where antibiotic protection is required. By simply putting asmuch water on the paper as can be absorbed, a solution with highbactericidal activity as well as detergent value is instantly producedwithout the need for measuring water or germicide; There is also no needto wash and rinse the object to be cleaned before using a germicide. Forexample, an operating table, a toilet seat, etc. can be cleaned andsanitized in one single operation. A soldier, a nurse, a stewardess,etc. can carry a germicide in the pocket in dry form. A two ply wipersize 13" X 18" which weighs only about 7 gms. will absorb about oneounce of water to produce about one ounce of bactericidal solutioncombined with an efiective alcohol type detergent and provide means ofapplying a cleaner and sanitizer in one operation.

In the manufacture of germicidal dustcloths made of cotton and the likeit has been customary to impregnate the cloth with an aqueous solutioncontaining a germicide which is then air-dried on the colth. Because ofthe nature of the structure of the cloth it could be subjected totreatment with the aqueous solution for long periods of time withoutdeleterious effect. In attempting to apply these aqueous processes tothe treatment of paper it was soon found that the results were notsatisfactory. It was found that from an aqueous solution of germicidethe paper could not absorb more than 1% water without altering itsstructure. The absorption of this small amount of water would not resultin the deposition of adequate amounts of germicide on the paper. It wasthus necessarytodevise a'methodto deposit an adequate amount ofgermicide on the paper.

It has now been found that paper will absorb sufficient germicide torender it useful as a germicidal or bacteriostatic paper withoutaltering the structure of the paper if the paper is treated with anon-aqueous vehicle in which the germicide is distributed.

A variety of non-aqueous liquid vehicles are known which are useful forthe purpose of the present invention. Among these may be mentioned lightoils, hydrocarbon distillates, solvents, monohydric alcohols, glycols,naphthas. The preferred liquid vehicles are the normally liquidhydrocarbons, cg. normally light liquid hydrocarbon oils, aliphaticnaphthas, Stoddard solvents, kerosenes (refined), paraffinichydrocarbons, natural mineral oil, pine oil, white mineral oil, etc.

Since the products of the present invention generally come in contactwith the skin, the non-aqueous liquid vehicles generally employed arethose that are non-toxic or non-irritating when the paper contacts theskin. Furthermore, the said vehicle obviously should be of such acharacter as not to deleteriously affect the bacteriostatic orgermicidal properties of the anti-bacterial agent employed.

All of the ingredients are preferably completely disper sible in thenon-aqueous vehicle so that subsequent agitation is not needed toredisperse the ingredients in the vehicle before use. By using theproper percentage of liquid vehicle a total all-side surface treatmentis assured. This is especially important when tissue paper is being usedwhich comes in 1, 2, 3, 4-ply or more.

For some purposes it is advantageous to incorporate in the paper certainagents. Thus, for example, there may be added to the liquid vehicle asilicone, wax or other agent which will be adsorbed on the paper whenthe paper is processed in accordance with this invention.

The germicidal and bacteriostatic agents which are preferably selectedfor the use in the present invention are the quaternary ammoniumcompounds which fulfill the requirements of stability, substantivity andlow degree of toxity. Of particular interest are the quaternary ammoniumcompounds of the following general structure wherein R R R and R areselected from the class consisting of alkyl, aryl, aralkyl andheterocyclic radicals and X is a halogen. Of special interest are thealkyl dimethyl benzyl ammonium chloride compounds. The alkyl group inthese compounds may be lower or higher alkyl groups.

A variety of water soluble germicidal or bacteriostatic chemicals areknown in the prior art which may be used in the present invention. Amongthese may be mentioned:

(27) (fl-Phenoxyethyl) dimethyl dodecyl ammonium H bromide (28) Octylphenoxy ethoxy ethyl dimethyl p-chlorobenzyl ammonium chloride (29)Dialkyl dimethyl ammonium chloride (30) Dialkyl dimethyl ammoniumbromide (31) Decamethylene-bis (decyl dimethyl ammonium) bromide (32)Trialkyl benzyl ammonium chloride (33) Myristamido propyldimethyl benzylammonium chloride (34) Myristyl-Y-picolinium chloride (35N-N-N-N'-tetramethyl-N-N-didodecyl-fl-hydroxypropylene diammoniumbromide With the present invention waxes, high percentage pine alcohols,oils and/or silicones can be added to the required degree and theresulting admixture remains clear indefinitely without separation. Thiswill permit the production of bacteriostatic paper for the manydifferent purposes intended in the invention.

A feature of the present invention is the fact that no separation of theessential constituents of the treating composition occurs. This is trueof the treating solution before it is applied to the paper or tissue aswell as the treating composition disposed on the paper or tissue. Sincethe treatment of the paper in accordance with the present invention mayinvolve contacting the paper with a treating solution for several days,it is very important that the components of the treating solution do notseparate out. Furthermore, since it may take several days for thetreating fluid to reach the deeper plies of paper, it is essential forthe proper treatment of these deeper plies that the constituents of thetreating solution do not separate out.

This property of stability of the present treating compositions isgreatly enhanced by incorporating in the treating solution a detergentof general formula 11 amon -omega wherein R is preferably a long chainalkyl radical and x has an average value of from 10 to 20. The bestresults are obtained with compounds of Formula 11 above wherein R is asaturated highly branched chain alkyl group of from 11 to 15 carbonatoms and particularly with the polyoxyethylene ethers of tridecylalcohols. By way of illus tration the following compounds which areuseful in the present invention may be mentioned: polyoxyethylene etherof tridecyl alcohol containing 12 oxyethylene groups per mole;polyoxyethylene ether of tetradecyl alcohol containing 16 oxyethylenegroups per mole; and polyoxyethylene ether of pentadecyl alcoholcontaining 14 oxyethylene groups per mole.

The relative proportions of germicide to the other ingredients containedin the treating solution may be varied considerably without departingfrom the spirit of this invention. In the preferred practice of theinvention the ratio of germicide to the weight of treated paper willvary in the range of from 0.3 to 0.6 part by weight of germicide to thetreated paper. When a detergent is employed, it is preferably used inthe range of l to 5 parts by weight of the liquid vehicle. The otheragents, e.g. silicones, oils, waxes or other polishing agents which areemployed, are preferably used in the range of about 1 to 5 parts byweight of liquid vehicle.

The following examples are further illustrative of the presentinvention. It is to be understood, however, that this invention is notlimited thereto.

EXAMPLE 1 7 One part by weight of alkyl dimethyl benzyl ammoniumchloride in water is mixed with 4 parts by weight of 100%polyoxyethylene tridecyl ether alcohol to form a 10% solution of saidalkyl dimethyl benzyl ammonium chloride. This solution is further usedto prepare the treating solution. The percentages of the materialsindicated below in this example are based on the total weight of thetreated paper product made in accordance with the present invention.Three percent of said 10% solution of quaternary ammonium compound wasmixed with a solution containing 17% hydrocarbon distillateand 1%silicones. This solution is used in test A below.

EXAMPLE 2 A solution was prepared by diluting one part of a 50% solutionof alkyl dimethyl benzyl ammonium chloride in water with 2 parts byweight of 100% polyoxyethylene tridecyl ether alcohol 2 and 2 parts byweight of pine oil containing terpene alcohol to form a 10% solution ofsaid alkyl dimethyl benzyl ammonium chloride. The percentages ofmaterials indicated below in this example are based on the total weightof the treated paper product made in accordance with this invention.Three percent of the 10% solution of quaternary ammonium compoundprepared above was mixed with 17% of hydrocarbon distillate and 1%silicones. his solution is used in test B below.

EXAMPLE 3 Three percent of the 10% solution of said quaternary ammoniumcompound prepared in Example 2 was mixed with a solution containing 5%carnauba wax, 12% hydrocarbon distfllate and 1% silicones. This solutionis' used in test C below.

1 50% alkyl (08431 dimethyl benzyl ammonium chloride.

2 Polyoxyethylene tridecyl ether alcohol, viscosity (cp. 25 C.) 80.

3 A colorless, light, non-odorous petroleum distillate, Sayboltviscosity F. 30/35.

4 Siliconcsnon-irritating-20 centistokes viscosity.

Zone of inhibition test results vs. Staph. aureus Average width of zoneof inhibition Sample No.

Inner Outer Section, Section, mm. mm.

A typical finish tissue sample contains the following:

Percent 0.3

C1261%, Cl-22%, GIG-11% related C8 to (118-437 While the invention hasbeen described with particular reference to specific embodiments, it isto be understood that it is not limited thereto, but is to be construedbroadly and restricted solely by the scope of the appended claims.

What is claimed is:

1. An article of manufacture useful in rendering surfaces germicidal andbacteriostatic, which comprises paper sfibstantially impre nated with awater soluble germicide distributed in a non-aqueous liquid carrierselected from the group consisting of light oils, hydrocarbondistillates, monohydric alcohols, glycols and naphthas.

2. An article of manufacture useful in wiping surfaces without anaqueous dispenser to render them germicidal and bacterio-static,comprising paper substantially impregnated with a water-solublegermicide distributed in a normally non-aqueous liquid hydrocarboncarrier.

3. An article of manufacture according to claim 2 wherein said liquidhydrocarbon carrier also contains a silicone and Wait.

4. An article of manufacture according to claim 2 wherein saidhydrocarbon carrier also contains a detergent of the formula RO(CH -CHO) H, wherein R is long-chain alkyl and x has an average value of fromto 20.

5. An article of manufacture according to claim wherein the Watersoluble germicide is a quaternary ammonium compound of the formula R2 R-l l-R la wherein R R R and R are selected from the group consisting ofalkyl, aryl, aralkyl and heterocyclic, and wherein X represents ahalogen.

6. An article of manufacture according to claim 5 wherein saidquaternary ammonium compound is alkyl-3- dimethyl benzyl ammoniumchloride.

7. An article of manufacture useful in wiping surfaces to render themgermicidal and bacteriostatic, comprising paper substantiallyimpregnated with a quaternary ammonium compound of the formula wherein RR R and R are selected from the group consisting of alkyl, aryl, aralkyland heterocyclic, and wherein X represents a halogen and apolyoxyethylene alkyl ether alcohol of the formula R0 (CH-C18 0) H,wherein R is long-chain alkyl and x has an average value of from 10 to20 distributed in a non-aqueous liquid hydrocarbon carrier.

8. An article of manufacture according to claim 7 wherein saidquaternary ammonium compound is alkyl dimethyl benzyl ammonium chlorideand said polyoxyethylene alkyl ether alcohol is polyoxyethylene tridecylether alcohol.

9. A method for the impregnation of a paper useful in wiping surfaceswithout a liquid dispenser to render them germicidal and bacteriostaticwhich comprises applying to any part of said paper a quantity ofnon-aqueous liquid vehicle in which is distributed a water soluble andgroups germicide selected from the group consisting of light oils,hydrocarbon distillates, monohydric alcohols, glycols, and naphthas, andsetting said treated paper aside for a predetermined period of time forsaid vehicle to penetrate throughout said paper.

10. A composition of matter useful in the treatment of paper to producean impregnated paper suitable for rendering surfaces germicidal andbacteriostatic, which comprises a non-aqueous liquid hydrocarbon vehiclehaving distributed therein a quaternary ammonium compound of the formulaR -N-R wherein R 1 R and R are selected from the group consisting ofalkyl, aryl, aralkyl and heterocyclic and wherein X represents a halogenand a polyoxyethylene alkyl ether alcohol of the formula RO(CH -CHO),,H, wherein R is a long-chain alkyl and x has an average value offrom 10 to 20.

11. An article of manufacture useful in wiping surfaces without additionof liquid dispenser to render the wiped surfaces germicidal andbacteriostatic, comprising a paper sheet substantially impregnated witha treating solution containing a water-soluble germicide, a silicone,and a detergent, distributed in a non-toxic, non-aqueous liquid carrierselected from the group consisting of light oil, hydrocarbondistillates, monohydric alcohols, glycols and naphthas, said paper sheethaving said germicide substantially uniformly distributed therein andbeing substantially dry to the touch.

12. An article of manufacture according to claim 11 wherein saidtreating solution contains about .3 to about .6% of said germicide, noless than 1% of said detergent, and no less than 1% of said silicone,all percentages being by weight of the treated paper.

13. A method of rendering a surface substantially germand bacteria-free,which comprises wiping said surface with a paper impregnated with anon-aqueous liquid vehicle in which is distributed a watersolublegermicide, said vehicle being selected from the group consisting oflight oils, hydrocarbon distillates, monohydric alcohols, glycols andnaphthas.

References Cited by the Examiner UNITED STATES PATENTS 1,969,900 8/1934Pickett 252-91 2,093,824 9/ 1937 Woronoff 252-91 2,251,328 8/1941 Ehret252-91 2,423,262 7/1947 Sowa 167-38.5 2,495,066 1/1950 Jones 252-912,544,732 3/1951 Shechmeister 167-84 2,566,092 8/1951 Mayfield 167-422,676,987 4/1954 Lewis et al 117-1385 X 2,702,780 2/ 1955 Lerner 167-842,756,647 7/1956 Thompson 252-91 2,812,332 3/1957 Pennino 16 7-3 8.52,933,431 4/1960 Sperouleas 167-84 2,951,788 9/1960 Lo 167-30 2,973,2972/ 1961 Bakkeren et a1. 167-84 X 3,138,533 6/1964 Heim et al. 167-84FOREIGN PATENTS 760,232 10/1956 Great Britain.

OTHER REFERENCES Soap and Sanitary Chemicals, June 1952, p. 159.

JULIAN S. LEVITT, Primary Examiner.

A. WOLMAN, MORRIS O. WOLK, FRANK CACCIA- PAGLIA, 1a., Examiners.

7. AN ARTICLE OF MANUFACTURE USEFUL IN WIPING SURFACES TO RENDER THEMGERMICIDAL AND BACTERIOSTATIC, COMPRISING PAPER SUBSTANTIALLYIMPREGNATED WITH A QUATERNARY AMMONIUM COMPOUND OF THE FORMULA